US10035099B2

US10035099B2 - CO2 removal device

Info

Publication number: US10035099B2
Application number: US15/301,099
Authority: US
Inventors: Kouhei Yoshikawa; Masato Kaneeda; Hidehiro Nakamura; Toshiaki Shirasaka
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Hitachi Ltd
Priority date: 2014-07-09
Filing date: 2015-07-08
Publication date: 2018-07-31
Also published as: WO2016006620A1; CA2941022C; EP3167951A1; JP2016016369A; CA2941022A1; CN106170330A; EP3167951A4; US20170014750A1; JP6413408B2; CN106170330B

Abstract

A CO₂removal device includes: a CO₂capturing material which captures H₂O and CO₂in a gas; a reaction container which contains the CO₂capturing material; an H₂O measuring unit for measuring the concentration of H₂O in the gas; an H₂O concentration adjustment device which adjusts the concentration of H₂O on the basis of information obtained by the H₂O measuring unit; a gas introduction path introducing the gas into the reaction container from the H₂O concentration adjustment device and bringing the gas into contact with the CO₂capturing material; a first gas discharge path discharging the gas from the reaction container after the gas has been brought into contact with the CO₂capturing material; and a second gas discharge path discharging the gas that has been desorbed from the CO₂capturing material from the reaction container.

Description

TECHNICAL FIELD

The present invention relates to: a device for removing CO₂from a gas containing CO₂, such as a combustion exhaust gas or the atmosphere; in particular a technology for reducing energy necessary for removing CO₂.

BACKGROUND ART

Global warming caused by the emission of a greenhouse effect gas is a global problem. As examples of the greenhouse effect gases, carbon dioxide (CO₂), methane (CH₄), and fluorocarbons (CFCs) are known. Among those gases, CO₂has the greatest impact and the establishment of a system for separating and removing CO₂from a thermal electric power plant, a steel plant, and the like has been an urgent issue.

Further, CO₂also has an affect on the human body. For example, when a gas containing CO₂of a high concentration is inhaled, a health hazard is caused and hence the control of a CO₂concentration is required in an enclosed space such as a room interior. In particular, a device for removing CO₂is required in an environment where outdoor air and indoor air are hardly interchangeable such as a space station. In other fields too, a system for removing CO₂is required because CO₂possibly has a negative effect during the manufacture of foods and chemical products.

Known examples of methods for solving the problem are a chemical absorption method, a physical absorption method, a membrane separation method, an adsorptive separation method, and a cryogenic distillation method. Among those methods, there is a CO₂separation and recovery method using a solid CO₂capturing material. In a CO₂removal system using a CO₂capturing material, CO₂is captured by introducing a CO₂containing gas into a capturing material container filled with the CO₂capturing material and bringing the CO₂containing gas into contact with the CO₂capturing material at the atmospheric pressure or an added pressure under a prescribed temperature condition. Successively, the captured CO₂is desorbed by heating the capturing material or depressurizing the interior of the capturing material container. The CO₂capturing material from which CO₂is desorbed is cooled or depressurized and the solid CO₂capturing material is initialized. The CO₂capturing material is used for removing CO₂from a CO₂containing gas by repeating capture and desorption as stated above. Further, it can be used also for separating and recovering CO₂at a high concentration from a CO₂containing gas by the above mechanism.

In such a device for capturing and removing CO₂, zeolite is mainly used as a CO₂capturing material. For example, Patent Literature 1 describes a CO₂removal method of adsorbing CO₂by bringing a gas containing CO₂into contact with a CO₂adsorptive agent of a zeolite type and successively desorbing CO₂by heating it.

CITATION LIST Patent Literature

Patent Literature 1: Japanese Translation of PCT international Application Publication No. JP-T-2010-527757

SUMMARY OF INVENTION Technical Problem

In the case of zeolite, the quantity of a captured CO₂reduces when it is brought into contact with a gas containing water vapor (H₂O) and hence H₂O is generally removed at a stage prior to CO₂capture. It is said for example that, in the method of capturing and removing CO₂described in Patent Literature 1, when a CO₂containing gas contains water vapor (H₂O), an H₂O concentration is reduced to preferably 400 Ppm or less and yet preferably to 20 ppm or less.

Some kinds of solid CO₂capturing materials are considered to have a favorable influence caused by bringing a gas containing H₂O into contact, for example the increase of the quantity of a captured CO₂, the reduction of temperature for desorbing CO₂, or both of them. In Patent Literature 1, however, those are not discussed and a device configuration using those is not described.

An object of the present invention is to provide a CO₂removal device allowing energy consumption to reduce.

Solution to Problem

A CO₂removal device according to the present invention includes: a CO₂capturing material to capture H₂O and CO₂in a gas; a reaction container which contains the CO₂capturing material; an H₂O measuring unit for measuring the concentration of H₂O in the gas; an H₂O concentration adjustment device which adjusts the concentration of H₂O on the basis of information obtained by the H₂O measuring unit; a gas introduction path for introducing the gas into the reaction container from the H₂O concentration adjustment device and bringing the gas into contact with the CO₂capturing material; a first gas discharge path for discharging the gas from the reaction container after the gas has been brought into contact with the CO₂capturing material; and a second gas discharge path for discharging the gas that has been desorbed from the CO₂capturing material from the reaction container.

Advantageous Effects of Invention

The present invention makes it possible to reduce an energy consumption in removing CO₂more than ever before.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph comparing the quantity of captured CO₂between the presence and absence of H₂O circulation in a cerium oxide according to Example 1.

FIG. 2 is a graph comparing the rate of CO₂desorbed during temperature rise between the presence and absence of H₂O circulation in a cerium oxide according to Example 1.

FIG. 3 is a graph comparing the correlation between an energy consumed for heating a capturing material and a temperature when CO₂is desorbed between the presence and absence of H₂O circulation in a cerium oxide according to Example 1.

FIG. 4 is a graph comparing the rate of CO₂desorbed during temperature rise between the presence and absence of H₂O circulation in a zirconium oxide according to Example 2.

FIG. 5 is a graph showing the correlation between the quantity of an absorbed H₂O and a partial pressure of H₂O in a cerium oxide according to Example 1.

FIG. 6 is a schematic configuration diagram showing a CO₂removal device (a fixed bed type) according to Example 3.

FIG. 7 is a schematic configuration diagram showing a CO₂removal device (a fixed bed type) according to Example 4, which enables CO₂to be continuously removed.

FIG. 8 is a schematic configuration diagram showing a CO₂removal device (a rotor type) according to Example 5.

FIG. 9 is a schematic configuration diagram showing a CO₂removal device according to Example 6, which uses two reaction containers and removes H₂O, CO₂, or both of them in a reaction container by switching a valve when capture saturation occurs in the other reaction container.

FIG. 10 is a schematic configuration diagram showing a CO₂removal device according to Example 7, which uses two reaction containers and reverses the direction of the circulation of a gas containing CO₂and H₂O and the direction of the circulation of a heating gas.

DESCRIPTION OF EMBODIMENTS

Best modes for carrying out the present invention are shown hereunder. The scope of the present invention however is not limited to the examples shown below.

The present inventors, as a result of earnestly studying the above problem, have found that, in a device for separating and removing CO₂, H₂O, or both of them from a gas containing CO₂and H₂O with a solid CO₂capturing material, the energy required for separating and removing CO₂can be reduced by: having the device comprise a capturing material capable of capturing H₂O and CO₂, a reaction container which contains the capturing material, an H₂O measuring unit for measuring the concentration of H₂O in a gas, an H₂O concentration adjustment device for adjusting the concentration of H₂O in the gas, a means for controlling the H₂O concentration adjustment device on the basis of information obtained by the H₂O measuring unit, a pipe for introducing a mixed gas containing CO₂and H₂O into the reaction container and bringing the mixed gas into contact with the capturing material, and a pipe for discharging the mixed gas from the reaction container after the mixed gas has been brought into contact with the capturing material; and leaving H₂O in the H₂O concentration adjustment device. This is presumably because the surface state of a solid changes by the circulation of H₂O, the state of capturing CO₂of a low desorption temperature can be formed, and an energy for heat required for desorbing CO₂can be reduced. Moreover, this is presumably because an energy required for removing H₂O can be reduced in comparison with the case of removing the whole quantity of H₂O.

Here, in this description, “removal” also intends that CO₂is recovered from a CO₂capturing material. Further, it also intends that purity is increased by recharging a recovered gas as an inlet gas.

A capturing material used for capturing CO₂and H₂O may be any material. The examples are a metal oxide, an activated carbon, a carbonate of alkali metal, a hydroxide of alkali metal, a layered double hydroxide, and a solid organic compound. The CO₂capturing material may be a single type or a combination of two or more types. Otherwise one may be used as a carrier and the other may be supported by using a method of impregnation or the like.

As a metal oxide, preferably a porous metal oxide or yet preferably an oxide or a complex oxide containing at least one metal selected from the group of Ce, a rare-earth metal other than Ce, and zirconium is used. When the combination of oxides is used as stated above, CO₂can be adsorbed even after H₂O is brought into contact and the CO₂desorption temperature can be lowered. This is presumably because, in such oxides, a hydroxyl group (—OH) is formed by the oxide surfaces reacting with H₂O and CO₂can be adsorbed on the surfaces in the shape of a hydrogen carbonate (—CO₃H) by the reaction between the functional group and CO₂. Known examples of methods of synthesizing the capturing material are the processing methods such as an impregnation method, a kneading method, a coprecipitation method, and a sol-gel method. For example, the capturing material may be precipitated by adjusting pH to 7 to 10 by adding a basic compound such as ammonia water, sodium hydroxide, or calcium hydroxide to a solution containing a nitrate of Ce. When an oxide is formed by precipitation, the oxide may be used directly or may be oxidized further by calcination.

As a metal oxide, an oxide obtained by calcining a layered double hydroxide may be used. The layered double hydroxide is a substance also called a hydrotalcite compound and is a material containing two or more metal elements and having a composition that can be represented by the following chemical formula (1). Here, in the chemical formula (1), M²represents a divalent metal ion such as Mg, Mn, Fe, Co, Ni, Cu, or Zn, M³represents a trivalent metal ion such as Al, Cr, Fe, Co, or In, and Aⁿrepresents an n-valent anion such as a carbonate ion, a nitrate ion, or a sulfate ion, respectively. As each of M², M³, and Aⁿ, a single ion may be used or two or more ions may be used.
M² _1-xM³ _x(OH)₂Aⁿ _x/n .yH₂O Chemical formula (1)

Known examples of methods for synthesizing a layered double hydroxide are the processing methods such as an impregnation method, a kneading method, a coprecipitation method, and a sol-gel method. For example, the layered double hydroxide may be precipitated by adjusting pH to 8 to 11 by adding a basic compound such as ammonia water, sodium hydroxide, or calcium hydroxide after sodium carbonate is added to a solution containing a nitrate of Mg and Al. The material obtained by the precipitation is a layered double hydroxide and hence it may be calcined in order to obtain a metal oxide or a complex oxide of metals. Any temperature may be adopted as the calcination temperature but a metal oxide can be obtained when it is calcined at 400° C. or higher, for example.

As other metal oxides and complex oxides of metals, silica (SiO₂) alumina (Al₂O₃), and zeolite may be used. Further, in order to increase a specific surface area, improve thermal resistance, and reduce the quantity of a used metal, it is also possible to support an oxide or a complex oxide containing at least one metal selected from the group of Ce, a rare-earth metal, and zirconium by silica, alumina, or zeolite.

An activated carbon used as a capturing material may be any material. In an activated carbon, when a nitrogen element (N) is contained in the interior, the basicity may increase and CO₂adsorption performance may improve in some cases and hence an activated carbon having a large N content may preferably be used sometimes. When such an activated carbon is synthesized, a method of bringing a gas containing ammonia (NH₃) into contact with an activated carbon or a method of synthesizing an activated carbon from an organic molecule containing N abundantly is conceivable.

As a solid organic compound, an organic compound having a basicity is preferably used and an example thereof is an organic compound having an amino group.

A reaction container filled with a CO₂capturing material, an H₂O capturing material, or both of them may be installed at the latter stage of another reaction container filled with another CO₂capturing material. Further, a method of installing a valve for switching a circulation route in a pipe part connecting reaction containers and using the reaction container of the latter stage when needed may be used. For example, when a capturing material capable of capturing both CO₂and H₂O is packed in the reaction container of the former stage, it is estimated that the capture of a gas of either CO₂or H₂O is saturated firstly and the gas is discharged from the exit of the reaction container. When the capture of CO₂is saturated firstly, a capturing material deteriorating CO₂capture performance when H₂O circulates may be used in the reaction container installed at the latter stage. Known examples of such a capturing material are zeolite and activated carbon. Meanwhile, when the capture of H₂O is saturated firstly, a capturing material of low CO₂capture performance may be used in the reaction container installed at the latter stage. Known examples of such a capturing material are silica and alumina. When the ratio of the concentrations of H₂O and CO₂in a gas is likely to vary and the capture of which gas is more likely to be saturated is unknown, a method of installing two reaction containers at the latter stage and selecting a used reaction container in accordance with the gas the capture of which is saturated may be adopted. When H₂O and CO₂can be removed only by the capturing container of the former stage, the treatment for desorbing H₂O and CO₂in the reaction container of the latter stage is not required and energy consumption can be reduced.

A known example of the combination of such reaction containers and such CO₂capturing materials is a configuration of installing a reaction container filled with a CO₂capturing material using an oxide or a complex oxide containing at least one metal selected from the group of Ce, a rare-earth metal other than Ce, and zirconium at the former stage and installing a reaction container filled with a CO₂capturing material using zeolite at the latter stage. When such a configuration is used, only the capture of CO₂is saturated in the reaction container of the former stage and, even when the gas is discharged from an exit, CO₂can be captured in the reaction container of the latter stage. Even when the capture of H₂O is saturated in the reaction container of the former stage and the gas is discharged from the exit, H₂O can be captured by zeolite at the latter stage, but generally zeolite adsorbs H₂O stronger than CO₂, and hence, in order to desorb H₂O from zeolite, the load required of heat and depressurization is higher than the case of desorbing CO₂. In such a configuration therefore, energy consumption is thou ht to be reduced rather by adjusting an H₂O concentration so that the capture of H₂O may not be saturated in the reaction container of the former stage.

A known example of the combination of such reaction containers and such CO₂capturing materials is a configuration of installing a reaction container filled with a CO₂capturing material using an oxide or a complex oxide containing at least one metal selected from the group of Ce, a rare-earth metal other than Ce, and zirconium at the former stage and installing a reaction container filled with an H₂O capturing material using silica or alumina at the latter stage. When such a configuration is used, only the capture of H₂O is saturated in the reaction container of the former stage and, even when the gas is discharged from an exit, H₂O can be captured in the reaction container of the latter stage. When the capture of CO₂is saturated in the reaction container of the former stage and the gas flows into the latter stage, since the CO₂capture performance of silica or alumina is low, CO₂may possibly be removed insufficiently. In such a configuration therefore, it is necessary to prevent the capture of CO₂from being saturated at the former stage by measuring a CO₂concentration distribution in the reaction container of the former stage or the like.

As such a mixed gas containing CO₂and H₂O, any gas may be used. Examples thereof are a boiler exhaust gas at a coal-fired power plant, a combustion exhaust gas of an automobile or the like, a gas generated by fermentation derived from a microorganism, the atmosphere, and the exhaled breath of a living thing. The composition is not limited but, in the case of a boiler exhaust gas or a combustion exhaust gas for example, in addition to CO₂and H₂O, nitrogen (N₂), oxygen (O₂) nitrogen oxide (NO_x), sulfur oxide (SO_x), carbon monoxide (CO), hydrocarbons such as methane (CH₄), and ashes are contained. In such gases, particularly NO_x, SO_x, and ashes are considered to deteriorate the CO₂capture performance of a capturing material and hence it is desirable to remove them beforehand when they are contained much.

As an H₂O concentration adjustment device in the CO₂removal device, any device may be used. For example, an H₂O concentration adjustment device using the temperature dependency of the saturated vapor pressure of H₂O includes a cooled condenser. The device is generally used for the purpose of reducing an H₂O concentration but may also be used for example for increasing the saturated vapor pressure of H₂O by adjusting temperature and increasing an H₂O concentration in a CO₂containing gas. Another example of the H₂O concentration adjustment device using the temperature dependency of the saturated vapor pressure of H₂O is a device of adjusting an H₂O concentration in a gas by feeding a gas in water (H₂O) in a liquid the temperature of which is adjusted. When such a device is used, a foaming machine such as a bubbler may be disposed in order to increase the contact area between water and a gas and improve efficiency. By using such a configuration, it is possible to control an H₂O concentration appropriately.

Another example of the H₂O concentration adjustment device is an H₂O concentration adjustment device which contains a material to capture H₂O. The material adsorbing H₂O may be any material. An example thereof is a porous material or a resin having the function of absorbing water. The components of the porous material are not limited but examples thereof are silica (SiO₂), alumina (Al₂O₃), zirconium oxide (ZrO₂), cerium oxide (CeO₂), a layered double hydroxide such as hydrotalcite, zeolite, an activated carbon, and an organic compound such as a resin material.

When such an adsorptive agent is used, it is estimated that H₂O is adsorbed when an H₂O concentration in a gas is high and inversely H₂O in a capturing material is desorbed when an H₂O concentration is low. Even when an H₂O concentration in a CO₂containing gas varies rapidly therefore, it is possible to inhibit the H₂O concentration in a gas touching a CO₂capturing material from varying.

A device to adjust an H₂O concentration may be a single device or may be used by combining two or more devices. For example, when an H₂O concentration is adjusted by using the temperature dependency of the saturated vapor pressure of H₂O, heat absorption or heat generation is caused by the vaporization of water (H₂O) or the condensation of water vapor and it is estimated that, when the quantity is large, the temperature difference from a heat transfer part increases and the temperature cannot be controlled appropriately. In such a case, it is desirable to control an H₂O concentration with a high degree of accuracy with two or more H₂O concentration adjustment devices.

As a device for measuring an H₂O concentration, any device may be used. Examples thereof are a dew-point hygrometer, an electric resistance hygrometer, a thermal conductivity hygrometer, and a wet-and-dry-bulb hygrometer. In order to adjust an H₂O concentration with an H₂O concentration adjustment device on the basis of a measured H₂O concentration, it is desirable to output an H₂O concentration as an electric signal and control the H₂O concentration adjustment device on the basis of the signal.

The site where a device for measuring an H₂O concentration is disposed is not limited and examples thereof are a method of measuring it on the upstream side of an reaction container filled with a CO₂capturing material, a method of measuring the quantity distribution of captured H₂O and measuring it in the interior of the packed bed of a CO₂capturing material in a reaction pipe in order to estimate capture saturation, and a method of measuring it on the downstream side of a reaction pipe in order to observe capture saturation.

An H₂O concentration in a mixed gas after it has been adjusted with the H₂O concentration adjustment device is not particularly limited but for example is preferably 20 ppm or more and may be 2,000 ppm or more.

An H₂O concentration may also be decided from a CO₂concentration. On this occasion, the mole ratio to CO₂is preferably not less than 0.5 to not more than 40. By controlling a mole ratio to CO₂to not less than 0.5, the surface state of a solid changes, a CO₂capture state of a low desorption temperature can be formed, and the energy required for heat necessary for desorbing CO₂can be reduced. By controlling a mole ratio to CO₂to not more than 40, it is possible to prevent the saturation of H₂O capture from occurring before the saturation of CO₂capture in a CO₂and H₂O capturing material.

A method of desorbing CO₂after CO₂is captured in a capturing material may be any method. Examples thereof are a temperature swinging method of raising the temperature of a capturing material and desorbing CO₂, a pressure swinging method of depressurizing the atmosphere of a capturing material and desorbing CO₂, and a temperature/pressure swinging method of using both the methods. Those desorption methods may be decided in consideration of the pressure, the CO₂partial pressure, and the temperature of a CO₂containing gas.

Examples of methods of heating a CO₂capturing material when a temperature swinging method is used are a method of bringing a heating medium such as a heated gas or liquid directly into contact with a CO₂capturing material, a method of circulating a heating medium such as a heated gas or liquid in a heat-transfer tube or the like and heating a CO₂capturing material by heat conduction from a heat-transfer surface, and a method of electrically generating heat by an electric furnace or the like and heating a CO₂capturing material.

When a heating gas of a high temperature is brought into contact with a capturing material, the heating gas may be decided in consideration of the application of the separation and removal of CO₂or the like. For example, when a concentration of CO₂recovered after desorption is intended to increase, CO₂may be used as a heating gas. When a heating gas and a desorbed gas are intended to be separated, H₂O the saturated vapor pressure of which varies largely by temperature may be used and H₂O may be removed by cooling a recovered gas. When no problem occurs even if a CO₂concentration in a desorbed gas reduces, N₂, O₂, the atmosphere (air), or the like, those being available at relatively low costs, may be used.

In a configuration of packing a CO₂capturing material and an H₂O capturing material in two or more reaction containers respectively, circulating a heating gas, and desorbing CO₂and H₂O, the heating gas may be circulated in the respective reaction containers individually. An advantage on this occasion is that a gas desorbed from a capturing material does not affect another capturing material. Otherwise, a configuration of, in the state of connecting reaction containers, introducing a heating gas from a reaction container, circulating the heating gas to another reaction container, and then discharging the heating gas may also be adopted. On this occasion, a gas used for heating a capturing material can be reused and hence energy consumption can be reduced. Another advantage is that the quantity of a used gas can be reduced. In the configuration, when a capturing material the CO₂capture performance of which deteriorates because H₂O flows in is used for example, it is desirable to control the circulation direction of a heating gas so that desorbed H₂O may not touch the capturing material. For example, when a cerium oxide is used as a CO₂capturing material of the former stage and zeolite is used as a CO₂capturing material of the latter stage, it is desirable to change the gas circulation direction between the time of capture and the time of desorption. A configuration of hardly circulating H₂O at the latter stage by circulating a gas containing CO₂and H₂O in the direction from the former stage to the latter stage is adopted when CO₂and H₂O are captured and a configuration of hardly bringing H₂O desorbed from a cerium oxide of the former stage into contact with zeolite of the latter stage by circulating the heating gas from the latter stage to the former stage is adopted during desorption, and thus the CO₂capture performance of the reaction container of the latter stage comes to be likely to be retained.

An example of a method of depressurizing the atmosphere when a pressure swinging method or a temperature/pressure swinging method is used is a mechanical means of using a pump, a compressor, or the like. An example used when the powdering of a material is influenced by vibration generated by the mechanical means or the like is a method of lowering a saturated vapor pressure by cooling water vapor in the atmosphere of a capturing material, condensing it, and depressurizing the atmosphere, etc. In addition, an example of a method of depressurizing the CO₂partial pressure of the ambient atmosphere of a CO₂capturing material is a method of circulating a gas other than CO₂. As a gas used on this occasion, a gas easily separable from CO₂is preferably used. In particular, a method of using water vapor is preferably used from the viewpoint of being easily condensed by cooling.

Examples of a method of pressurizing the ambient atmosphere of a CO₂capturing material include a method of pressurizing mechanically by a pump, a compressor or the like, or a method of introducing a gas having a higher pressure than the ambient atmosphere.

A capturing material may be used in any shape. Examples thereof include a method of forming a capturing material in a powdery shape, a pelletal shape, or a granular shape, and a method of supporting a capturing material by a honeycomb. Those shapes may be decided in view of a required reaction speed, a pressure loss, and a CO₂purity in a desorbed gas. Further, with regard to a void ratio, the void ratio may be lowered when the CO₂purity in a desorbed gas is increased. For example, when a granular shape is formed and a void ratio is small, there is the disadvantage that the pressure loss increases but, since the quantity of a gas other than CO₂remaining in the voids reduces, there is the advantage that the CO₂purity in a recovered gas is improved. Meanwhile, when a capturing material is supported by a honeycomb, a void ratio is high and hence a pressure loss can be reduced, but the quantity of a gas other than CO₂remaining in the voids increases and hence there is the disadvantage that the CO₂purity in a desorbed gas deteriorates.

A reaction container filled with a CO₂capturing material may adopt any configuration and any operating method. An example thereof is a fixed-bed method of filling the interior of a reaction container with a granular or powdery CO₂capturing material and changing a gas introduced into the CO₂capturing material container and the temperature and pressure in the reaction container without moving the CO₂capturing material itself. The configuration has the advantage that performance degradation caused by friction in the capturing material or between the capturing material and the reaction container can be kept low because the movement of the capturing material is low. Further, since a packing density can be increased, it is conceived that a void ratio can be lowered and a removed CO₂quantity per unit capacity can be increased. On the other hand, when a temperature swinging method of heating a capturing material by circulating a heating gas and desorbing CO₂is applied by using the configuration, the switching of a circulating gas is required and hence there is the disadvantage that the configuration of a pipe and a valve becomes complicated.

As a method of moving a CO₂capturing material itself without switching a circulating gas or the like, for example there is a rotor method of disposing a honeycomb rotor by which a CO₂capturing material is supported, a reaction container, and a partition plate for Partitioning gas circulation in the reaction container and separating the interior of the reaction container into a CO₂capturing zone, a CO₂heating and desorbing zone, and a CO₂capturing material cooling zone, and the like in accordance with a gas circulated. By rotating a honeycomb, it is possible to move the CO₂capturing material in the interior to the respective zones and apply the cycle of CO₂capturing, CO₂heating and desorbing, and CO₂capturing material cooling. In the configuration, the CO₂capturing material is supported by the honeycomb and thus the configuration has the advantage that the CO₂capturing material itself wears less and the performance degradation can be suppressed low. Further, since the switching of a circulating gas is not required, the configuration of a pipe and a valve is simplified. Furthermore, it is possible to decide the dimensions of the respective zones by changing the disposition of the partitioning plate and thus the ratios of a CO₂capturing time, a heating and desorbing time, a cooling time, and the like can be decided easily. On the other hand, there are the disadvantages that a void ratio is high, a removed CO₂quantity per unit volume is low, and a CO₂concentration in a CO₂desorbed gas is low. When two or more capturing materials are used in the method, it is possible: to install two or more reaction containers and use honeycomb rotors by which the respective capturing materials are supported in the respective reaction containers; or to divide one honeycomb rotor into the sites for supporting the respective capturing materials and support two or more capturing materials. An example thereof is a method of supporting a CO₂capturing material containing a cerium oxide on the upstream side of the honeycomb rotor and supporting a CO₂capturing material containing zeolite on the downstream side. In the configuration, it is desirable to circulate a gas containing CO₂and H₂O in the direction from the upstream side to the downstream side and a heating gas in the direction from the downstream side to the upstream side, from the viewpoint of inhibiting H₂O from touching zeolite and the CO₂capture performance from degrading.

As another method of moving a CO₂capturing material itself without switching a circulating gas and the like, there is a fluidized bed method of repeating capture and desorption by installing a CO₂capturing reaction container in which a CO₂containing gas circulates and a CO₂capturing material heating container in which a gas for heating a capturing material circulates and moving a granular or powdery capturing material between the containers with the power of a conveyer or a blower. In the configuration, since the switching of a circulating gas is not required, the configuration of a pipe and a valve is simplified. Further, since different void ratios can be set between the time of capture and the time of desorption, for example, it is possible to set a void ratio so as to be low at the time of desorption and increase a CO₂concentration in a CO₂desorbed gas. Meanwhile, since the capturing material itself moves, performance is considered to deteriorate by wear when it is used for a long time. When the gas circulation rate of a boiler exhaust gas or the like is very large, a method of blowing a capturing material upward by a gas in place of a conveyer may be used. On this occasion, a simple configuration can be obtained because the number of mechanical parts reduces in comparison with a conveyer.

Examples according to the present invention are hereunder explained in detail.

Here, with regard to cerium nitrate hexahydrate (Ce(NO₃)₃.6H₂O) and ammonia water 28% by weight, the materials manufactured by Wako Pure Chemical Industries, Ltd. are used.

Example 1

(CO₂Capturing Material Using Cerium Oxide)

Cerium nitrate hexahydrate of 26.05 g is dissolved in purified water of 1,080 g while being stirred intensely at room temperature. pH is set at 9.0 by dropping an ammonia aqueous solution 28% in weight while the aqueous solution is stirred. The aqueous solution is left to stand for one hour after stirred for eight hours and a sediment is accumulated by washing and filtering. Successively, the sediment is dried at 120° C. in a drying furnace and calcined for one hour at 400° C. in an electric furnace under the atmosphere and the obtained cerium oxide is used as a CO₂capturing material.

Example 2

(CO₂Capturing Material Using Zirconium Oxide)

Zirconium oxide (RSC-100) manufactured by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD. is used as a CO₂capturing material.

(CO₂Adsorption Test—Absence of H₂O Circulation)

The test conditions in the case of adsorbing CO₂without H₂O circulation are shown hereunder.

Forming and Disposition

A CO₂capturing material is pelletized at 200 kgf with a press machine by using a die 40 mm in diameter, crushed, and then granulated into grains of 0.5 to 1.0 mm with a sieve. Successively, the CO₂capturing material of 1.0 ml is determined by a measuring cylinder and fixed in a quartz-glass reaction pipe.

Heat Pretreatment:

While He is circulated at a rate of 150 ml/min, the temperature of the CO₂capturing material is raised to 400° C. by an electric furnace and retained for one hour and thus impurities and the gas adsorbed in the capturing material are removed.

Cooling:

After the heat pretreatment, the temperature of the CO₂capturing material is lowered to 50° C. by cooling.

Adsorption:

While the specimen temperature is retained at 50° C. by the electric furnace, the quantity of captured CO₂is measured by CO₂pulse capture test. A mixed gas of 10 ml comprising CO₂of 12% by volume and He of 88% by volume is introduced for two minutes at pulsed intervals of four minutes as a sample gas and the CO₂concentration at the exit of the reaction pipe is measured by gas chromatography. The pulsed introduction is carried out until CO₂measured at the reaction pipe exit is saturated. Further, He is used as the carrier gas.

Heat and Desorption:

The specimen temperature is raised to 400° C. at a rate of 10° C./min in the electric furnace and the quantity of desorbed CO₂is measured.

(CO₂Adsorption Test—Presence of H₂O Circulation)

The test conditions in the case of adsorbing CO₂after H₂O is circulated are shown. The quantity of the absorbed CO₂is measured by a method similar to the measurement method in the case of “CO₂adsorption test—absence of H₂O circulation” except that H₂O circulation treatment is applied after cooling and before adsorption in this case.

H₂O Circulation Treatment:

In a bubbler container containing water of 25° C., He is circulated at a rate of 150 ml/min for one hour. The temperature of a CO₂capturing material during the treatment is set at 50° C. by the electric furnace.

FIG. 1 is a graph comparing the quantity of captured CO₂between the presence and absence of H₂O circulation in a CO₂capturing material according to Example 1. By the H₂O circulation, the quantity of captured CO₂reduces by about 10 percent.

FIG. 2 is a graph comparing the rate of CO₂desorbed during temperature rise between the presence and absence of H₂O circulation in the CO₂capturing material according to Example 1. When the H₂O circulation is present, the quantity of desorbed CO₂is large at relatively low temperatures of 50° C. to 200° C. and almost the whole CO₂is desorbed before the temperature reaches 200° C. When the H₂O circulation is absent in contrast, the CO₂desorption does not complete even when the temperature is raised to 300° C. It has been found from the result that the H₂O circulation creates the effect of lowering a CO₂desorption temperature.

FIG. 3 shows a heat quantity required for raising the temperature of a cerium oxide and shows the heat quantity per unit desorbed CO₂quantity. The specific heat of the cerium oxide is set at 382 J/K·kg and a heat quantity H required for raising temperature is calculated by the following expression. Here, in the present test, the bulk density of the cerium oxide is set at 1.41 (kg/L), a quantity of desorbed CO₂is represented by Q_d, and a desorption temperature is represented by T_d, and a heat quantity H is calculated by the following expression (2).
H=1,000 (g)/44 (g/mol)×1,000/Q_d(mmol/L)×1.41 (kg/L)×(T_d−50)(K)×382 (J/K·kg) (2)

It has been found from the result that the energy required for heating can be reduced more in the case of the presence of the H₂O circulation.

FIG. 4 is a graph comparing the rate of CO₂desorbed during temperature rise between the presence and absence of H₂O circulation in a CO₂capturing material according to Example 2. When the H₂O circulation is present, the quantity of desorbed CO₂is large at 50° C. to 200° C. and it has been found from the result that the H₂O circulation creates the effect of lowering a CO₂desorption temperature.

(Evaluation Method of Specific Surface Area)

With regard to a cerium oxide according to Example 1, the adsorption isothermal line of nitrogen is measured at −196° C. by a BET (Brunauer-Emmett-Teller) method and a specific surface area is measured. As pretreatment, heating is applied at 200° C. while vacuuming is applied. The specific surface area of Example 1 is 130 m²/g.

(Measurement of H₂O Adsorption Isothermal Line)

The H₂O adsorption isothermal line of a cerium oxide according to Example 1 is measured. As pretreatment, heating is applied at 200° C. while vacuuming is applied. Successively, cooling is applied while vacuuming is applied and H₂O is adsorbed while the temperature of the specimen is retained at 25° C.

(Calculation of H₂O Monomolecular Layer Adsorption Quantity)

An adsorption quantity Q_m1for forming an H₂O monomolecular layer on the surface of a cerium oxide according to Example 1 is calculated. A specific surface area obtained by the BET method is represented by S_A, the Avogadro's number N_Ais set at 6.02×10²³, and an adsorption sectional area of H₂O is set at 1.25×10⁻¹⁹m², and an adsorption quantity Q_mlis calculated by the following expression (3).
Q_ml=S_A÷1.25×10⁻¹⁹÷6.02×10²³×1,000 (3)

As a result of the calculation, the calculated H₂O monomolecular layer adsorption quantity Q_m1is 1.8 mol/kg.

FIG. 5 is a graph showing the H₂O adsorption isothermal line of a cerium oxide according to Example 1. From the result, the H₂O partial pressure that allows the quantity of H₂O adsorbed in the cerium oxide according to Example 1 to be not less than an adsorbed CO₂quantity (300 mol/L÷1.41 kg/L=0.22 mol/kg) is not more than 0.002 kPa. An H₂O concentration may be about 20 ppm in order to secure the H₂O partial pressure in the atmospheric pressure. That is, to introduce a gas of the H₂O concentration is thought to be the condition for securing reaction when H₂O/CO₂is not less than 1 in terms of mole ratio. A hydroxyl group (—OH) of 1 mole is thought to be necessary on a surface in order to form a hydrogen carbonate of 1 mole. Assuming that surface oxygen (O) of 1 mole reacts with H₂O of 1 mole and a hydroxyl group of 2 moles is generated as a mechanism of forming a hydroxyl group, H₂O/CO₂only have to be not less than 0.5 in terms of mole ratio and it is estimated that the reaction advances sufficiently as long as H₂O/CO₂is not less than 1.0 in terms of mole ratio. As long as the H₂O concentration is 20 ppm as stated above, H₂O/CO₂can exceed 1.0 in terms of mole ratio. Further, the formation of a hydroxyl group is thought to be further promoted if the surface of a cerium oxide is covered with an H₂O monomolecular layer. An H₂O partial pressure necessary for an adsorbed H₂O quantity to be equivalent to an H₂O monomolecule adsorption quantity is 0.2 kPa. An H₂O concentration may be about 2,000 ppm in order to secure the H₂O partial pressure in the atmosphere.

In the above calculation, an adsorbed CO₂quantity increases if the specific surface area of a ceriumoxide increases, but an adsorbed H₂O quantity is thought to increase also in proportion to the specific surface area, and hence the correlation of the H₂O concentration obtained on the basis of Example 1 is thought to be able to be used also for another material.

The correlation between an H₂O concentration and an adsorbed H₂O quantity varies in accordance with the temperature of a capturing material but H₂O has the nature of showing nearly an equivalent adsorbed H₂O quantity if a saturated vapor pressure and a relative pressure P/P0 are equivalent at the temperature. When the temperature of a capturing material varies therefore, an H₂O concentration may be decided on the basis of a saturated vapor pressure at the temperature.

Example 3

FIG. 6 shows an example of applying a CO₂capturing material according to Example 1 to a fixed bed type CO₂removal device and introducing a CO₂removed gas into a room interior.

The CO₂removal device shown in FIG. 6 includes a pipe 301 for circulating a gas 101 containing H₂O and CO₂, a condenser 501, a pipe 305 for discharging water 201 condensed at the condenser 501, an H₂O densitometer 601, a means 1001 for imputing a signal from the H₂O densitometer 601 to a computer 1002, a means 1003 for outputting a signal for controlling the condenser 501 from the computer 1002, a valve 401 for controlling the circulation of the gas 101, a reaction container 701, a CO₂capturing material 801 containing a cerium oxide according to Example 1 and being packed granularly in the reaction container 701, a pipe 302 for circulating the gas in the reaction container to a room interior, a valve 402 for controlling the gas circulation in the pipe 302, a heater 901, a pipe 303 for circulating a heating gas 103 taken in from the atmosphere to the reaction container 701, a valve 403 for controlling the gas circulation in the pipe 303, a pipe 304 for discharging the gas in the reaction container to the atmosphere, and a valve 404 for controlling the gas circulation in the pipe 304.

When CO₂is captured, by opening the

valves

401 and 402 and closing the

valves

403 and 404, CO₂and H₂O in the gas 101 containing H₂O and CO₂are captured in the CO₂capturing material 801 and the gas from which H₂O and CO₂have been removed circulates to the room interior.

When CO₂captured in the CO₂capturing material is desorbed, by opening the

valves

403 and 404 and closing the

valves

401 and 402, the gas 103 taken in from the atmosphere is heated by the heater 901 and circulates in the reaction container 701, the CO₂capturing material 801 is heated, and the captured CO₂desorbs. The desorbed gas circulates in the pipe 304 and is discharged to the atmosphere.

Example 4

FIG. 7 shows an example of applying a CO₂capturing material according to Example 1 to a fixed bed type CO₂removal device and continuously circulating a CO₂removed gas to a room interior with two reaction containers.

FIG. 7 shows a configuration formed by adding a reaction container 702, a CO₂capturing material 802 containing a cerium oxide and being packed granularly in the reaction container 702, a pipe 306 for circulating a gas 101 containing H₂O and CO₂to the reaction container 702, a valve 406 for controlling the gas circulation in the pipe 306, a pipe 307 for circulating the gas in the reaction container to a room interior, a valve 407 for controlling the gas circulation in the pipe 307, a pipe 308 for circulating a heating gas 103 taken in from the atmosphere to the reaction container 702, a valve 408 for controlling the gas circulation in the pipe 308, a pipe 309 for discharging the gas in the reaction container to the atmosphere, and a valve 409 for controlling the gas circulation in the pipe 309 to the configuration according to Example 3.

When CO₂is captured in the reaction container 701 and desorbed in the reaction container 702, the

valves

401, 402, 408, and 409 should be opened and the

valves

403, 404, 406, and 407 should be closed. When CO2 is desorbed in the reaction container 701 and captured in the reaction container 702, the

valves

403, 404, 406, and 407 should be opened and the

valves

401, 402, 408, and 409 should be closed. By the configuration and the operation method, the gas from which CO₂has been removed can be circulated to the room interior continuously.

Example 5

FIG. 8 shows an example of using a rotor type CO₂removal device and introducing a CO₂removed gas into a room interior.

In the CO₂removal device shown in FIG. 8, a honeycomb rotor 801 supporting a CO₂capturing material containing a cerium oxide according to Example 1 is disposed in the interior of a reaction container 701 and the route of gas circulation is restricted by a partition plate 702 in the reaction container. The

zones

701A, 701B, and 701C in the reaction container 701 are gas circulation ranges determined by the partition plate 702. The position of the partition plate 702 does not vary even when the honeycomb rotor 801 rotates but the site of the honeycomb rotor touching a gas varies by the rotation of the honeycomb rotor 801. In the configuration, CO₂is captured by circulating a gas containing H₂O and CO₂in the zone 701A (capturing zone), CO₂is desorbed by circulating a gas heated at a heater 901 in the zone 701C (desorbing zone), and the CO₂capturing material is cooled by circulating a gas 103 taken in from the atmosphere in the zone 701B (cooling zone).

The CO₂removal device includes a pipe 301 for circulating a gas 101 containing H₂O and CO₂to a zone 701A in a reaction container 701, a condenser 501, a pipe 305 for discharging condensed water 201 from the condenser, an H₂O densitometer 601, a means 1001 for inputting a signal from the H₂O densitometer to a computer 1002, a means 1003 for outputting a signal from the computer 1002 in order to control the condenser 501, the reaction container 701, a rotatable honeycomb rotor 801 being installed in the reaction container 701 and supporting a CO₂capturing material, a partition plate 702 installed in the reaction container for partitioning gas circulation, a pipe 302 for circulating a gas discharged from the zone 701A to a room interior, a pipe 303 for circulating a gas 103 taken in from the atmosphere to a zone 702B, a heater 901, a pipe 304 for circulating a gas discharged from the zone 701B to the heater 901, a pipe 306 for circulating a gas discharged from the heater 901 to a zone 701C, and a pipe 307 for emitting a gas discharged from the zone 701C to the atmosphere.

In the device, by circulating a gas containing H₂O and CO₂to the zone 701A, H₂O and CO₂are captured by the CO₂capturing material in the honeycomb rotor and the gas from which H₂O and CO₂are removed circulates to the room interior. By the rotation of the honeycomb rotor, a part that has captured CO₂moves to the zone 7010, the heated gas circulates, and thus CO₂is desorbed. A heated part from which CO₂is desorbed moves to the zone 701B and is cooled by a gas taken in from the atmosphere. The cooled part moves to the zone 701A and captures CO₂again.

In the configuration, since the gas 103 taken in from the atmosphere is used for cooling the honeycomb rotor, the gas is heated. Since the gas is further heated by the heater 901 and used, the load of the heater 901 can be reduced.

Example 6

FIG. 9 shows an example of removing H₂O and CO₂with two or more CO₂capturing materials and two or more reaction containers.

In a CO₂removal device shown in FIG. 9, a cerium oxide and zeolite are used as the CO₂capturing materials.

The device includes a pipe 301 for circulating a gas 101 containing H₂O and CO₂to a reaction container 701, a CO₂capturing material 801 containing a cerium oxide according to Example 1 and being packed in the reaction container 701, a condenser 501, a pipe 305 for discharging condensed water from the condenser, an H₂O densitometer 601, a means 1001 for inputting a signal from the H₂O densitometer 601 to a computer 1002, a means 1003 for outputting a signal from the computer 1002 in order to control the condenser 501, a pipe 302 for circulating a heating gas, a pipe 303 for circulating a gas discharged from the reaction container 701 to a room interior, a valve 403 for controlling the gas circulation in the pipe 303, a pipe 304 for emitting a gas from the reaction container 701 to the atmosphere, a valve 404 for controlling the gas circulation in the pipe 304, an H₂O densitometer 602 for further measuring the H₂O concentration in the gas discharged from the reaction container 701, a CO₂densitometer 603, a reaction container 702, a capturing material 802 containing zeolite and being packed in the reaction container, a pipe 306 for circulating a gas from the reaction container 701 to the reaction container 702, a valve 406 for controlling the gas circulation in the pipe 306, a pipe 307 for circulating a gas discharged from the reaction container 702 to the room interior, a valve 407 for controlling the gas circulation in the pipe 307, a pipe 309 for emitting a gas from the reaction container 702 to the atmosphere, a valve 409 for controlling the gas circulation in the pipe 309, a pipe 308 for circulating a heating gas to the reaction container 701, and a valve 408 for controlling the gas circulation in the pipe 308.

For example, when the capture of only H₂O is likely to be saturated in the CO₂capturing material 801, a capturing material selectively capturing H₂O should be packed as the capturing material 802 in the reaction container 702 of the latter stage. Inversely, when the capture of only CO₂is likely to be saturated in the CO₂capturing material 801, by packing a capturing material selectively capturing CO₂as the capturing material 802 in the reaction container 702 of the latter stage, a gas from which H₂O and CO₂have been removed can be circulated stably to the room interior.

Example 7

FIG. 10 shows an example of removing H₂O and CO₂with two or more CO₂capturing materials and two or more reaction containers.

In the example, a cerium oxide and zeolite are used as the CO₂capturing materials.

In FIG. 10, a CO₂capturing material 801 containing a cerium oxide is used in a reaction container 701 and a CO₂capturing material containing zeolite is used in a reaction container 702. Whereas the flow of gas circulation is directed from the reaction container 701 to the reaction container 702 when H₂O and CO₂are removed from a gas containing H₂O and CO₂, the opening and closing of valves are adjusted so that the flow of heating gas circulation may be directed from the reaction container 702 to the reaction container 701 when H₂O and CO₂are removed by the circulation of a heating gas. The purpose is to prevent H₂O from being captured intensively in zeolite by bringing H₂O desorbed from the CO₂capturing material 801 containing a cerium oxide into contact with zeolite in the reaction container 702.

REFERENCE SINGS LIST

101: Gas containing H₂O and CO₂,
103: Heating gas,
301, 302, 303, 304: Pipe,
401, 402, 403, 404: Valve,
501: Condenser,
601: H₂O densitometer,
701: Reaction container,
801, 802: CO₂capturing material,
901: Heater.

Claims

The invention claimed is:

1. A CO₂removal device comprising:

a CO₂capturing material which captures H₂O and CO₂in a gas;

a reaction container which contains the CO₂capturing material;

an H₂O measuring unit for measuring the concentration of H₂O in the gas;

an H₂O concentration adjustment device which adjusts the concentration of H₂O on the basis of information obtained by the H₂O measuring unit;

a gas introduction path for introducing the gas into the reaction container from the H₂O concentration adjustment device and bringing the gas into contact with the CO₂capturing material;

a first gas discharge path for discharging the gas from the reaction container after the gas has been brought into contact with the CO₂capturing material; and

a second gas discharge path for discharging the gas that has been desorbed from the CO₂capturing material from the reaction container.

2. The CO₂removal device according to claim 1, wherein the CO₂capturing material contains at least one kind selected from the group consisting of a metal oxide, an activated carbon, a carbonate of alkali metal, a hydroxide of alkali metal, a layered double hydroxide, and a solid organic compound.

3. The CO₂removal device according to claim 2, wherein the CO₂capturing material contains an oxide or a complex oxide containing at least one metal element selected from the group consisting of cerium, a rare-earth metal other than cerium, and zirconium.

4. The CO₂removal device according to claim 1, comprising two or more the reaction containers.

5. The CO₂removal device according to claim 4, wherein:

at least one of the reaction containers has a capturing material containing an oxide or a complex oxide containing at least one metal element selected from the group consisting of cerium, a rare-earth metal other than cerium, and zirconium; and

the other reaction container of the reaction containers has a capturing material containing at least one metal oxide selected from the group consisting of silica, alumina, and zeolite.

6. The CO₂removal device according to claim 5, wherein, when a capturing material containing an oxide or a complex oxide containing at least one metal element selected from the group consisting of cerium, a rare-earth metal other than cerium, and zirconium is defined as a capturing material A, a capturing material containing at least one metal oxide selected from the group consisting of silica, alumina, and zeolite is defined as a capturing material B, and CO₂, H₂O, or both of them is/are removed from the gas, a circulation of the gas is directed from the capturing material A to the capturing material B.

7. The CO₂removal device according to claim 1, further comprising a heating means to heat the CO₂capturing material.

8. The CO₂removal device according to claim 1, wherein:

a heating fluid is configured so as to touch the CO₂capturing material; and

the heating fluid is a fluid containing at least one gas selected from the group consisting of CO₂, water vapor, N₂, a combustion exhaust gas, and a gas obtained by being heated after taken in from the atmosphere.

9. The CO₂removal device according to claim 8, wherein a direction of a circulation of the gas is identical to a direction of a circulation of the heating fluid.

10. The CO₂removal device according to claim 8, wherein a direction of a circulation of the gas is opposite to a direction of a circulation of the heating fluid.

11. The CO₂removal device according to claim 7, comprising a device for circulating a heating medium of a temperature higher than the CO₂capturing material in a heat transfer device and heating the CO₂capturing material by the heat transferred from the heat transfer device.

12. The CO₂removal device according to claim 11, wherein the high temperature heating medium is a gas containing water vapor.

13. The CO₂removal device according to claim 7, wherein the heating means is a device to heat by electric power.

14. The CO₂removal device according to claim 1, further comprising a depressurizing device for depressurizing the reaction container.

15. The CO₂removal device according to claim 1, further comprising a pressurizing device for pressurizing the reaction container.

16. The CO₂removal device according to claim 1, wherein the gas has a pressure higher than the atmospheric pressure.